CN106947023A - The preparation method of low temperature flow state styrene indene resin - Google Patents
The preparation method of low temperature flow state styrene indene resin Download PDFInfo
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- CN106947023A CN106947023A CN201710140932.XA CN201710140932A CN106947023A CN 106947023 A CN106947023 A CN 106947023A CN 201710140932 A CN201710140932 A CN 201710140932A CN 106947023 A CN106947023 A CN 106947023A
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- indene resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/02—Polymerisation in bulk
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Abstract
The invention discloses a kind of preparation method of low temperature flow state styrene indene resin, comprise the following steps：(1) by indenes and olefin, raw material mixed liquor is obtained；Gained raw material mixed liquor and catalyst are added in polymeric kettle, solvent-free continuous polymerization reaction is carried out, obtains polymer fluid；(2) catalyst in polymer fluid obtained by removing step (1), carries out vacuum distillation by the polymer fluid of Removal of catalyst, to remove unreacting material, obtains styrene indene resin.It is in a liquid state under the styrene indene resin normal temperature generated, compatibility is good, easy to use.Also, regulation indenes can obtain different viscosities product with olefin ratios as needed, expand the application of styrene indene resin, it is expected to replace import, realizes production domesticization；In addition, the preparation method technique is simple, polymerizing condition is gentle, and environmental pollution is few, and production efficiency is high, and it is 60 200 DEG C, conversion ratio more than 80%, suitable mass production to control polymerization temperature.
Description
Technical field
The invention belongs to Aromatic Petroleum Resins fabricating technology field, more particularly to a kind of low temperature flow state styrene-
The preparation method of indene resin.
Background technology
Styrene indene resin is external a kind of excellent rubber tackifier and softening agent developed in recent years, and it adds
To enter improve after rubber its viscosity, intensity and extensibility, and because styrene indene resin sizing material initial viscosity and viscosity are kept
It is all relatively good, and the physical and mechanical properties and cure time of sizing material are had no adverse effect, it is that the first choice for producing radial is helped
Agent.Current China relies primarily on import using the product, therefore develops the product, is allowed to domesticize, significant.
Existing styrene indene resin production process is mostly to use solvent polymerization method, intermittent reaction generation, causes production efficiency
It is low, big for environment pollution, the shortcomings of complex operation, viscosity are high or uncontrollable.It is main using C5 or C9 cuts such as CN1048505C
Raw material, is carried out under catalyst action after cold poly- (cation low temperature polymerization) or hot polymerization (high temperature radical polymerization), polymerisation
Styrene indene resin is extracted from reaction solution.But because C5 and C9 fractional compositions are complicated, it is deeper to obtain color of resin after polymerization,
Softening point is high, limits the use scope of product.In the research of low softening point styrene indene resin, such as patent
CN101691439B, low-temperature resins are not direct outputs, it is necessary to which later stage modification or compounding, production is complicated, and its viscosity number is also
It is uncontrollable.Therefore, have that a kind of viscosity to be developed is controllable, environment-friendly, the simple low viscosity styrene-indene resin of technique preparation
Method, to improve product quality, reduces manufacturing cost, realizes production domesticization.
The content of the invention
The technical problem to be solved in the present invention be overcome the deficiencies in the prior art there is provided a kind of viscosity it is controllable, environment-friendly,
The preparation method for the low temperature flow state styrene indene resin that technique is simple, production efficiency is high, polymerizing condition is gentle.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of preparation method of low temperature flow state styrene indene resin, comprises the following steps：
(1) by indenes and olefin, raw material mixed liquor is obtained；Gained raw material mixed liquor and catalyst are added into polymeric kettle
In, solvent-free continuous polymerization reaction is carried out, polymer fluid is obtained；
(2) catalyst in polymer fluid obtained by removing step (1), vacuum distillation is carried out by the polymer fluid of Removal of catalyst,
To remove unreacting material, styrene indene resin is obtained.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that described without molten in the step (1)
The temperature of agent continuous polymerization reaction is 60~200 DEG C.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (1), the catalysis
Agent is acidic catalyst.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (1), the acidity
Catalyst includes mixed acid or the lewis acid of sulfuric acid, phosphoric acid, sulfuric acid and phosphoric acid.
Wherein, lewis acid includes AlCl3Or BF3·Et2O。
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (1), the catalysis
The quality of agent is the 0.1%~15% of raw material mixed liquor.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (1), the raw material
Mixed liquor, the mass ratio of the indenes and alkene is 1:0.1~1.0.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (1), the alkene
Including styrene or α-methylstyrene.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (2), removes step
(1) technical process of the catalyst in gained polymer fluid is：Add calcium hydroxide stirring 15-60min in polymer fluid to neutralize, to thing
Material PH=6.5-8.0 is filtrated to get resin liquid.
The preparation method of above-mentioned low temperature flow state styrene indene resin, it is preferred that in the step (2), the decompression
The technical process of distillation is：
The vacuum distillation under vacuum -0.07~-0.09MPa of above-mentioned resin liquid is removed after unreacting materials to 240 DEG C is
Obtain liquid styrene-indene resin under normal temperature.
Compared with prior art, the advantage of the invention is that：
1st, the preparation method of low temperature flow state styrene indene resin of the invention, using indenes and alkene as raw material, without it
His solvent, is carried out under solvent-free polymeric reaction, the styrene indene resin normal temperature generated under the catalytic action of catalyst in stream
Hydrodynamic state, compatibility is good, easy to use.Also, regulation indenes can obtain different viscosities product with olefin ratios as needed, produce
It is product viscosity stabilization, controllable, the application of styrene indene resin has been expanded, has been expected to replace import, realizes production domesticization.
2nd, the preparation method of low temperature flow state styrene indene resin of the invention, using one-pot successive reaction, production efficiency
It is high.Technique is simple, and polymerizing condition is gentle, and environmental pollution is few, 80~120 DEG C of polymerization temperature of control, conversion ratio more than 80%,
Suitable mass production.
Embodiment
Below in conjunction with specific preferred embodiment, the invention will be further described, but not thereby limiting the invention
Protection domain.
Embodiment 1：
By indenes and styrene by 1: 0.4 mixing, raw material mixed liquor is obtained；Gained raw material mixed liquor and sulfuric acid are pressed 1: 1%
Add in polymeric kettle, it is 90~100 DEG C to control reactor polymerization temperature, carries out solvent-free continuous polymerization reaction, obtains polymer fluid,
Polymer fluid overflow collection sampling detection conversion ratio is 90%；Calcium hydroxide stirring is added in polymer fluid and is neutralized to PH=6.5-7.0,
It is filtrated to get to be slowly warming up to after interior 230 DEG C of temperature under resin liquid, control vacuum -0.085MPa after stirring 30min and stops distillation, it is cold
But normal temperature liquid styrene-indene resin, viscosity is obtained afterwards：3000mPaS (25 DEG C), product yield is 86%.
Embodiment 2：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：By indenes and styrene by 1: 0.2 mixing, obtain
Normal temperature liquid styrene-indene resin, viscosity：8000mPaS (25 DEG C), product yield is 88%.
Embodiment 3：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：By indenes and styrene by 1: 0.6 mixing, obtain
Normal temperature liquid styrene-indene resin, viscosity：800mPaS (25 DEG C), product yield is 87%.
Embodiment 4：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Styrene is changed to α-methylstyrene by 1:
0.4 mixing, obtains normal temperature liquid styrene-indene resin, viscosity：4000mPaS (25 DEG C), product yield is 88%.
Embodiment 5：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Sulfuric acid is changed to phosphoric acid, normal temperature liquid is obtained
Styrene indene resin, viscosity is 2500mPaS (25 DEG C), and product yield is 73%.
Embodiment 6：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Sulfuric acid is changed to AlCl3, obtain normal temperature liquid
Styrene indene resin, viscosity is 600mPaS (25 DEG C), and product yield is 65%.
Embodiment 7：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Sulfuric acid is changed to BF3·Et2O, obtains benzene second
Alkene-indene resin, viscosity is 12000mPaS (25 DEG C), and product yield is 88%.
Embodiment 8：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：Raw material mixed liquor and sulfuric acid ratio are changed to 1:
3%, obtain normal temperature liquid styrene-indene resin, viscosity：3500mPaS (25 DEG C), product yield is 85%.
Embodiment 9：
The present embodiment is substantially the same manner as Example 1, and it only difference is that：By polymerization temperature control at 110~120 DEG C,
Obtain normal temperature liquid styrene-indene resin, viscosity：2500mPaS (25 DEG C), product yield is 84%.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of low temperature flow state styrene indene resin, comprises the following steps：
(1) by indenes and olefin, raw material mixed liquor is obtained；Gained raw material mixed liquor and catalyst are added in polymeric kettle, entered
The solvent-free continuous polymerization reaction of row, obtains polymer fluid；
(2) catalyst in polymer fluid obtained by removing step (1), vacuum distillation is carried out by the polymer fluid of Removal of catalyst, with de-
Except unreacting material, styrene indene resin is obtained.
2. the preparation method of low temperature flow state styrene indene resin according to claim 1, it is characterised in that the step
Suddenly in (1), the temperature of the solvent-free continuous polymerization reaction is 60~200 DEG C.
3. the preparation method of low temperature flow state styrene indene resin according to claim 1 or 2, it is characterised in that described
In step (1), the catalyst is acidic catalyst.
4. the preparation method of low temperature flow state styrene indene resin according to claim 3, it is characterised in that the step
Suddenly in (1), the acidic catalyst includes mixed acid or the lewis acid of sulfuric acid, phosphoric acid, sulfuric acid and phosphoric acid.
5. the preparation method of low temperature flow state styrene indene resin according to claim 4, it is characterised in that the step
Suddenly in (1), the quality of the catalyst is the 0.1%~15% of raw material mixed liquor.
6. the preparation method of low temperature flow state styrene indene resin according to claim 5, it is characterised in that the step
Suddenly in (1), the raw material mixed liquor, the mass ratio of the indenes and alkene is 1:0.1~1.0.
7. the preparation method of low temperature flow state styrene indene resin according to claim 6, it is characterised in that the step
Suddenly in (1), the alkene includes styrene or α-methylstyrene.
8. the preparation method of the low temperature flow state styrene indene resin according to any one of claim 4~7, its feature exists
In in the step (2), the technical process of the catalyst in polymer fluid obtained by removing step (1) is：Hydrogen-oxygen is added in polymer fluid
Change calcium stirring 15-60min to neutralize, resin liquid is filtrated to get to material PH=6.5-8.0.
9. the preparation method of low temperature flow state styrene indene resin according to claim 8, it is characterised in that the step
Suddenly in (2), the technical process of the vacuum distillation is：
Above-mentioned resin liquid is obtained under vacuum -0.07~-0.09MPa after vacuum distillation to 240 DEG C of removing unreacting materials
Liquid styrene-indene resin under normal temperature.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710140932.XA CN106947023B (en) | 2017-03-10 | 2017-03-10 | The preparation method of low temperature flow state styrene indene resin |
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| CN201710140932.XA CN106947023B (en) | 2017-03-10 | 2017-03-10 | The preparation method of low temperature flow state styrene indene resin |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368798A (en) * | 2022-07-19 | 2022-11-22 | 扬州市祥华新材料科技有限公司 | Electrochemical aluminum laser layer coating and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691439A (en) * | 2009-10-12 | 2010-04-07 | 宫相勤 | Method for preparing resin with good low temperature fluidity |
-
2017
- 2017-03-10 CN CN201710140932.XA patent/CN106947023B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691439A (en) * | 2009-10-12 | 2010-04-07 | 宫相勤 | Method for preparing resin with good low temperature fluidity |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115368798A (en) * | 2022-07-19 | 2022-11-22 | 扬州市祥华新材料科技有限公司 | Electrochemical aluminum laser layer coating and preparation method thereof |
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| CN106947023B (en) | 2019-03-01 |
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Effective date of registration: 20210421 Address after: 213000, No. 8, North Road, Xinbei District, Jiangsu, Changzhou Patentee after: Changzhou Huada nano material technology Co.,Ltd. Address before: 213000, No. 8, North Road, Xinbei District, Jiangsu, Changzhou Patentee before: JIANGSU HUADA CHEMICAL GROUP Co.,Ltd. |
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